On the structure of the N,N′ -dimethylpropyleneurea and dimethylsulfoxide solvated gallium(III) and indium(III) ions and bromide complexes in solution and solid state, and the complex formation of the gallium(III) and indium(III) bromide systems in N,N′ -dimethylpropyleneurea

Abstract

The structures of the N,N′-dimethylpropyleneurea (DMPU) solvated gallium(III) and indium(III) ions have been determined in DMPU solution by means of EXAFS. The gallium(III) ion is five-coordinate with a mean Ga–O bond distance of 1.924(5) Å, while the larger indium(III) ion is octahedrally coordinated with a mean In–O bond distance of 2.146(3) Å. The complex formation equilibria in DMPU for the gallium(III) and indium(III) bromide systems have been studied calorimetrically at 298 K. Three relatively strong complexes are formed in the indium(III) bromide system in DMPU, whereas no stability constants could be established in the gallium(III) bromide system as the heats of complex formation were very close to zero. Gallium(III) bromide is present as DMPU solvated GaBr 3 complexes in solution with three equatorial Ga–Br bonds at 2.328(3) Å, and two Ga–O bonds at 1.92(3) Å in the apical positions of a distorted trigonal bipyramid. The DMPU solvated indium(III) bromide has the same configuration with a mean In–Br bond distance of 2.510(3) Å, and two In–O bonds at 2.201(6) Å. Indium(III) binds three bromides and three Me 2SO molecules through the oxygen atoms in octahedral fac-configuration with mean In–Br and In–O bond distances of 2.630(3) and 2.211(15) Å, respectively.